2-nitro-4-benzenesulfonamido chlorobenzenes

ABSTRACT

A keratin fiber dye composition which comprises a solvent and a dyeing amount of a dye compound having the formula:   in which n is a whole number between 2 and 6 inclusive, and R2 and R3, which may be identical or different, are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and with the nitrogen atom adjacent R2 and R3 may form morpholino and piperidino, each R1, R2, R3 having 1-6 carbon atoms on their alkyl portion, AND THE PROCESS OF DYEING KERATIN FIBERS.   IN WHICH R&#39;&#39; is selected from the group consisting of methyl and NO2, and R&#39;&#39;&#39;&#39; is selected from the group consisting of hydrogen and lower alkyl, having 1-6 carbon atoms, AND R1 is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, and   D R A W I N G IN WHICH R is selected from the group consisting of lower alkyl, hydroxy alkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, haloalkyl, aminoalkyl, aminodialkyl, alkylaminodialkyl, alkyl morpholino, alkyl piperidino, having 1-6 carbon atoms on each mentioned alkyl portion, Z is selected from the group consisting of

United States Patent [191 Kalopissis et a1.

[ Nov.'l8, 1975 l 2-NITRO-4-BENZENESULFONAM1DO CHLOROBENZEN ES [75] Inventors: Gregoire Kalopissis, Paris; Andree Bugaut, Boulogne-sur-Seine; Vahan Zorayan, Enghien-les-Bains, all of France [73] Assignee: LOreal, Paris, France [22] Filed: Apr. 20, 1973 [21] Appl. No.: 352,994

Related US. Application Data [62] Division of Ser. No. 78,923, Oct. 7, 1970, Pat. No. 3,742,048, which is a division of Ser. No. 728.750,

May 13. 1968, Pat. No. 3,617,164.

[30] Foreign Application Priority Data OTHER PUBLICATIONS J. Chem. Soc. (1967) 1136-1138, Corbett et al.

Primary Examiner-Sherman D. Winters Assistant ExaminerS. D. Winters Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT A keratin fiber dye composition which comprises a solvent and a dyeing amount of a dye compound having the formula:

NHR

in which R is selected from the group consisting of lower alkyl, hydroxy alkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, haloalkyl, aminoalkyl, aminodialkyl, alkylaminodialkyl, alkyl morpholino, alkyl piperidino, having 1-6 carbon atoms on each mentioned alkyl portion, Z is selected from the group consisting so R'-c-R" 0 1 o in which R is selected from the group consisting of methyl and N0 and R is selected from the group consisting of hydrogen and lower alkyl, having 1-6 carbon atoms,

and R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, and

in which n is a whole number between 2 and 6 inclusive, and R and R which may be identical or different, are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and with the nitrogen atom adjacent R and R may form morpholino and piperidino, each R R R having 1-6 carbon atoms on their alkyl portion,

and the process of dyeing keratin fibers.

1 Claim, No Drawings Z-NITRO-4-BENZENESULFONAMIDO CHLOROBENZENES V This is a division of application Ser. No. 78,923 filed Oct. 7, 1970 now US. Pat. No. 3,742,048, which in turn is a division of Ser. No. 728,750, filed May 13, 1968, now U.S. PatNo. 3,617,164.

It is an object of the present invention to provide a new chemical compound responding to the formula:

. /8 I H \z N02 mm in which R represents a lower alkyl, which may or may not be substituted, and in particular a hydroxyalkyl, carboxyalkyl, carbethoxyalkyl, carbamylalkyl, halogenoalkyl or aminoalkyl radical. The aminoalkyl may, or may not be substituted on the amine functiom the nitrogen atom of which may form part ofa heterocyclic ring. In the above formula Z may be an radical, or a radical, with R representing a hydrogen atom, a methyl group, or an NO group, and R" representing a hydrogen atom, or a lower alkyl, while R represents a lower alkyl, a lower hydroxyalkyl, a lower .alkoxyalkyl, or a 2)" ent, represent a hydrogen atom, a lower alkyl, or a lower hydroxyalkyl, while the nitrogen atom adjacent R and R may form therewith a heterocyclic radical such as a morpholino or piperidino radical, the radicals of the alkyl portions of the radicals R R R R R having 1-6 carbon atoms.

Another object of the present invention is to provide now quaternary derivatives corresponding to the compounds of formula (1), when these compounds have a quaternizable tertiary amine function.

It should be noted that the compounds of formula (1) are particularly adapted to be used to dye keratinic fibers in general, and especially. hair. They have an excellent affinity for keratinic fibers, good stability when exposed to light and inclement weather,- andare readily soluble in water. l

A further object. of the present invention is to provide a composition for dyeing human hair essentially characterized by the fact that it comprises, in solution, at least one dye selected-from the group consistingof the compounds responding to formula (I) and their quaternary derivatives.

The dyeing compositions according to the invention are preferably simple aqueous solutions having a pH value lying generally between 4 and 10, and preferably between 7 and 10.

Moreover, the dyeing compositions according to the invention may comprise variousingredients currently used in hair dyeing compositions, such for example as organic solvents, thickening agents, detergents, emollients, perfumes and lacquers. The dyes according to the invention may also be mixed with each other and with other dyes. such as nitro dyes, azo dyes, anth r'aqui-- none dyes, or any other type of dye conventionally used to dye hair.

The application of t hese dyeing compositions to the hair does not necessitate the addition of an oxidizing agent. The time of contact with the hair may vary within broad limits, but falls preferably between 5 and,

30 minutes. The temperature at which said composi; tions are applied may also be varied, but they are preferably used at room temperature. The concentration of the dye may be varied within broad limits, but lies preferably between 0.1% and 3% by weight.

It is a further object of the present invention to provide a method of dyeing hairessentially characterized by'the fact that a dyeing composition as hereinbefore defined is applied to the hair for between 5 and 30 minutes, and the hair is then washed, rinsed, and dried.

The present invention also comprises a method of preparing the compounds of formula (I) essentially characterized by the factthat, in the first step parahalogenometanitranilines or arylsulfonamides re sponding to the formula:

so n' i (III) 3 in which X and R have the significances hereinbefore indicated. Then, in a second step, the compound according to formula III is amidificd to transform it into a derivative responding to the'formula:

NRZ

in which X and R have the significances hereinbefore indicated and Z represents either an radical, 'in'which R has the significances hereinbefore indicated, or a l radical in which R" has the significance hereinbefore indicated. This is followed by a third step in which the compound of formula IV is reacted with an amine having the formula R,NH in which R 'has the significance hereinbefore indicated.

The compounds responding to formula (I) may be quaternized in a conventional manner, using a quaternizing agent such as methyl sulfate or an alkyl or aryl halide.

It is also an object of the present invention to provide the intermediates obtained in the course of the above described process, per se. In particular, it is desired to obtain chemical compounds responding to the formula:

NHR

:2 (III) and their salts (particularly their hydrohalides) as well as the chemical compounds responding to the formula:

N02 (Iv) and their salts (particularly their hydrohalides). In these formulae R, X and Z have the significances hereinbefore indicated.

The present invention also encompasses the methods of making the newintermediates responding to formulas (Ill) and (IV). These processes consist of the first and second steps of the method of making the compound of formula (I), as hereinbefore described.

In order that the invention may be better understood, several examples of methods of making the intermediates of formulas (Ill) and (IV) and the final compound of formula (I), as well as several dyeing compositions made with the compounds of formula (I) will now be described.

In the first series of examples, the preparation of several compounds responding to formula (III) will be described.

EXAMPLE I Preparation of 2-nitro-4-N-B-hydroxyethylamino chlorobenzene by direct alkylation A mixture containing 0.070 mol (12 g) of 2-nitro-4- amino chlorobenzene is heated in a boiling water bath with 0.14 mol (25 g) of glycol bromohydrin, 10 cc of water and 7 g of calcium carbonate. After heating for two hours, 0.14 mols of 70% glycol bromohydrin and 7 g of calcium carbonate is added and the heating continued for another two hours. After cooling, 150 cc of normal hydrochloric acid is poured in, and the mixture filtered. After alkalizing with ammonia, drying yields l3.5 g of a product which contains a little 2- nitro-4-N-B-hydroxyethylamino chlorobenzene. After recrystallization in a mixture of water'and ethanol, 2- nitro-4-N-B-hydroxyethylamino chlorobenzene is obtained. This melts at 72C and is the same as the product hereinafter described in Example 4.

EXAMPLE 2 Preparation of 2-nitro-4-N-(B-diethylaminoethyl)-amino chlorobenzene by direct alkylation This product is prepared by adding diethylaminoethyl hydrobromide to a solution of 2-nitro-4-amino chlorobenzene in the presence of calcium carbonate in water and alcohol which has first been brought to reflux. After keeping this at reflux for nine hours, it is boiled dry. The filtrate is cooled, and the desired product is; isolated in the form of its monohydrobromide. The corresponding base prepared from this monohydrobromide is an oil, which is dissolved hot in a 1/10 normal solution of hydrochloric acid. After cooling, drying yields the monohydrochloride of 2-nitro-4-N- (B-diethylaminoethyl)-4-amino chlorobenzene which after recrystallization in l/lO normal hydrochloric acid, melts and decomposes at 191C, and is the same as the product hereinafter described in Example 5.

EXAMPLE 3 Preparation of N-methyl-parachlorometanitraniline par alkylation with arylsulfonamides First step alkylation.

0.4 mol (l25' g) of 2-nitro-4-ben2enesulfonylamino chlorobenzene is dissolved in 600 cc of a normal sodium hydroxide solution at 30C. 1.6 mols cc) of methyl sulfate is added little bylittle, while keeping the temperature between 35 and 40C and the pH value near 9 by successive additions of a normal sodium hydroxide solution. The reaction mixture is then left to stand for six hours at room temperature. Cooling, drying and washing then yields 138 g of crude 2-nitro-4-N- methyl-N-benzene sulfonylamino benzene which, after recrystallization in ethyl acetate, melts at 1 19C. Analysis of this product shows the following results:

Analysis Calculated for Found C,H-,N,O Cl

C 45.08 44.87 44.96 H 7: 3.72 3.84 3.87 N92 15.01 15.15-15.25

EXAMPLE 4 Preparation of N-B-hydroxyethyl-parachlorometanitraniline by alkylation of an arylsulfonamide First step: Alkylation 0.097 mol (30 g) of 2-nitro-4-N-benzene-sulfonylamino chlorobenzene is dissolved in 195 cc of a one-half normal sodium hydroxide solution which has first been brought to 60C. While maintaining the reaction mixture at this temperature, 0.5 mol (33.3 cc) of glycol chlorohydrin is added drop by drop while stirring vigorously. A five times normal sodium hydroxide solution is added simultaneously to keep the pH between 10.5 and 11. The mixture is maintained at 60C for about 5 hours and then left standing for 12 hours at room temperature. Drying and washing with water yields 34 g of 2-nitro-4-(N-B-hydroxyethyl-N-benzenesulfonyl)-amino chlorobenzene which, after recrystallization in methanol, melts at l 19C. Analysis of the product yields the following results:

Calculated for Analysis Found l-l lil z s C Second step: Hydrolysis 0.0056 mol (2 g) of 2-nitro-4-(N-B-hydroxyethyl-N- benzenesulfonyl)-amino chlorobenzene is heated for an hour and a half in a boiling water bath in 25 cc of concentrated hydrochloric acid. After cooling and dilution, this is alkalized with ammonia and drying yields 55 0.9 g of N-B-hydroxyethyl-parachlorometanitraniline which, after recrystallization in benzene, melts at 72C. Analysis of the product yields the following results:

Analysis Calculated for Found c..H,.N,0,c1 v

c '7; 44.34 A 44.61 44.61 H 7: 4.15 4.08 4.23 N '71 12.93 13.04 12.93

EXAMPLE 5 Preparation of 2-nitro-4-(N-B-diethylaminoethyl)amino chlorobenzene monohydrochloride by alkylation of an aryl sulfonamide A First step: alkylation.

' 0.1 mol (31.25 g) of 2-nitro-4-N-benzenesulfonylamino chlorobenzene is dissolved in 100 cc of a twice normal sodium hydroxide solution which has first been brought to 60C. While maintaining the reaction mixture at this temperature 0.16 mol (27.5 g) of diethylaminoethylchloride hydrochloride in aqueous solution, is added drop by drop, together with cc of a twice normal sodium hydroxide solution which serves to keep the pH sufficiently alkaline. This reaction mixture is kept at 60C for 30 minutes, cooked, acidified with concentrated hydrochloricacid, and, when then dried, yields 36.5 g of the desired product in the form of its hydrochloride. This crude hydrochloride is purifled by crystallization in water, and then converted by addition of a twice normal solution of sodium hydroxide into 2-nitro-4-(N-B-diethylaminoethyl-N-benzenesulfonyl) amino chlorobenzene which. after vacuum drying on P 0 melts at 43C. The analysis of this product yields the following results:

Analysis Calculated for Found C H N O S Cl C 52.49 52.25 52.33 H% 5.35 5.17-5.26 N 10.21 10.40 10.45

Analysis Calculated for Found CIZHIWNSOZ C 46.75 46.88 46.86 H 6.16 6.33 6.32 N 13.63 13.45 13.65

In a second series of examples the method of preparing several intermediate compounds responding to formula (IV) will now be described.

EXAMPLE 6 Preparation of- (N methyl-N acetyl) parachloromctanitraniline 0.19 mol of N-methyl-parachlorometanitranilinc; prepared as set-forth in example 3, is dissolved in 70 cc of acetic anhydride. This is heated for 15 minutes in a boiling water-bath, and poured into 700 cc of water. Drying then yields 35 g of 2.-nitro-4-(N-methyl-N- acetyl)amine chlorobenzene, which melts at 114C.

- EXAM PLE 7 Preparation of 2-nitro-4-(N-methyl N-benzenesulfonyl)-amino chlorobenzene 0.19 mol (35.5 g) of N-methyl-parachlorometanitraniline prepared as set forth in example 3 is dissolved in 175 cc of pyridine. 0.5 mol (88.25 g) of benzenesulfochloride isadded. After heating to reflux for minutes the. mixture is cooled, and drying yields 60 g of 2- nitro-4-(N-methyl-N-benzenesulfonyl)-amino chlorobenzene which, after recrystallization in ethyl acetate, melts at 119C.

EXAMPLE 8 Preparation of 2-nitro-4-(N-benzenesulfonyl-N-B-diethylaminoethyl)- amino chlorobenzene 0.02 mol (6.16 g) of 2-nitro-4-N-(B-diethylaminoethyl)amino chlorobenzene is dissolved in 30 cc of pyridine. 0.04 mols, (7.06 g) of benzenesulfochloride .is added. After heating to reflux for 20 minutes, this is poured into 100 cc of cold water, and subsequent drying yields 8.9 g of 2-nitro-4-(N-benzenesulfonyl-N-diethylaminoethyl)-amino chlorobenzene monohydrochloride in practically pure form. This hydrochloride, when treated with a twice normal sodium hydroxide solution, yields the corresponding base which, after washing with water and prolonged vacuum drying, melts at 43C.

EXAMPLE 9 Preparation of 2-nitro-4-( N-acetyl-N-B-acetoxyethyl )-amino chlorobenzene 0.04 mol (8.6 g) of 2-nitro-4-/3-hydroxethylamino chlorobenzene is heated for an hour in a boiling water bath while insolution in cc of acetic anhydride. After driving off the excess of acetic anhydride under vacuum, the residue is dissolved by heating it in a mixture containing 40% hexane and 60% benzene. After cooling, drying yields 10.5 g of 2-nitro-4-(N-acetyl-N- B-acetoxyethyU-amino chlorobenzene which, after recrystallization in the benzene hexane mixture, melts at 60C. Analysis of this product yields the following results:

Analysis Calculated for Found C H N O Cl C 47.92 48.00 48.04 N% 9.31 9.50 9.45 H7: 4.32 4.45 4.40

In a third series of examples the preparation of certain compounds responding to formula (1) will now be described.

EXAMPLE 10 Calculated for Found The above-described monohydrochloride is treated for two hours with a twice normal sodium hydroxide solution, while stirring vigorously. The sodium hydroxide solution is then extracted with methylisobutyl ketone. The methylisobutylketone, which contains the desired product in solution in the form of its base, is washed with water, dried on sodium sulfate, filtered, and the solvent driven off under vacuum to yield the base in the form of a red oil.

EXAMPLE 1 1 Preparation of methyl-B-[ N-( 2-nitro-4-N -methyl-N '-benzenesulfonyl-amino)phenyll-aminoethyl methyldiethylammonium sulfate In order to carry out this synthesis, the product obtained at the end of example 10 of the present application is used. 0.148 mol (60 g) of l-N-B-diethylaminoethylamino-2-nitro-4-(N'-methyl-N'-benzenesulfonyl- )amino-benzene is dissolved in 600 cc of cold chlorobenzene and 0.164 mol (16 cc) of methyl sufate is added drop by drop, while stirring. The reaction mixture is left standing for 24 hours at room temperature. Drying and washing with a little chlorobenzene then yields 74 g of the desired ammonium salt, which melts at 137C. Analysis of this product yields the following results:

Calculated for Found Analysis N at 10.53 s *7. |2.03

EXAMPLE 12 Preparation of 1-N-B-hydroxyethy1amino-2-nitro-4-(N -methyl-N- benzenesulfonyl)amino benzene 0.153 mol (50 g) of 2-nitro-4-(N-methyl-N-benzenesulfonyl)amino' chlorobenzene which has been prepared as described-in Example 7 is introduced little by little, while stirring, into 3.06 mols (184 cc) of ethanolaminc, which has first been heated to 95C. The reaction mixture is held for 15 minutes in a boiling water. bath and cooled. 2.5 liters of ice water containing 425 cc of concentrated hydrochloric acid is then added. Drying yields 48 g of practically pure lN-B-hydroxythylamino-2-nitro-4-(N'-methy1-N'-benzenesulfonyl)- amino benzene which, after recrystallization in alcohol,

melts at 141C. Analysis of this product yields the following results:

Analysis Calculated for Found ls fl il fi EXAMPLE 13 Preparation of i 1-N-'y-methoxypropylamino-2-nitro-4-(N-methyl-N benzenesulfonyl)amino benzene 0.1 inol (32.65 g) of 2-nitro-4-(N rnethyl-N-benzenesulfonybamino chlorobenzene which has been prepared as indicated in Example 7,,is introduced little by little, while stirring, into2 mols (178 g) of y-methoxy-propylamine whichhas firstbeen heated to 95C. The reaction mixture is kept in a boiling water bath for twenty minutes, cooled, and 200 ccv of ice water is then poured in The.product is an orange-colored oil, which crystallizes very.,.easi1y. Drying yields 37 g of practicallypure 1-Ny-methoxy-z propylarriin6-2-nitro-4-(N-methyl-Nbenzenesulfony1)amino benzene, which, after recrystallization in alcohol, melts at 76C. Analysis of this product yields the following results:

Analysis Calculated for "Found II ZI R S N7: 11.08 11.19-11.28 s 8.44 2.44 --s.ss

EXAMPLE '14 Preparation of 1-'y-methoxypropylamino-2-nitro 4-(N-methyl-N- acetyl)-amino benzene 0.1 mol (22.9 g) of N-methyl-parachlorometanitraniline which has been prepared as described in Example 6, is introduced, while stirring, into 1.5 mols (134 g) of 'y-methoxypropylamine whichfhas first been heated to 95C. This reaction mixture is kept at 95C for 20 minutes, cooled and poured into 1.250 litersof ice water. This is acidified with hydrochloric acid, dried, and washing with water 7 yields 25 g of 1 -'y-methoxypropylamino-2-nitro-4-(N-methyl-N-acetyl)amino benzene which, after recrystallization, melts in toluene at 90C. Analysis of this product yields thefollowing results: 1

Analysis Calculated for Found u a a C 74 55.52 55.77- 55.54 H 92 I 6.76 6.85 6.83 N"/ 14.95 l .l l l5.0l

EXAMPLE Preparation br 1 N-B-diethy1aminoethylamino-2-nitro 4-( N -B-diethylaminoethyl-Nfibenzeries'ulfonyl)amirio benzene 0.05 mol (20.5 g) of 2 nitro-4-(:N-B diethylaminoethyl-N-benzenesulfonyl)-arnino chlorobenzene,'prepared as described in- Example -8,' is introduced into 0.5 mol (58 g) *of diethylethylenediamine' which has first been heated'to 95C. The reactionlmixtur 'e' is 'kept at'this temperature for 30. minutes.,The excess of aliphatic amine is driven under vacuumand'the'oily residue is poured into 200 cc ofwater. Tliis' yieldsthe desired product in the form of a thick oil. The water is decantedfthe oil is dissolved in normalhydrochloric acid;

7 the hydrochloric acid solution is filtered and alkalized with a five times normal sodium hydroxide solution. The desired product is then fextracted, using methylisobutylcetone and the solvent driven off under vacuum, yielding 22.6 g of practically pure l-N-B-diethylaminoethylamino-2-nitro-4-(N '-B-diethylamino- 'ethyl-N'-benzenesulfonyl)amino benzene in the form of a very thick oil. Analysis of this product yields the following result:

Analysis Calculated for Found 24 a1 s 4S I EXAMPLE. l6

* Preparation of 1-N-'y-hydroxypropylamino-2-nitro-4-(N-methyl-N- Analysis Calculated for Found CI2HI7NGOJ C 53.93 54.14 53.93 H X 6.37 6.37 6.54 N 7: 15.73 15.91-15.80

EXAMPLE 17 Preparation of v I I 1-N-B-diethylaminoethylamino-2-nitro-4-( N '43-. hydroxyethyl-N-benzenesulfonyl)-amino benzene 0.070 mo] (25 g)-of 2-nitro -4-(N-B-hydroxyethyl-N- benzenesulfonyD-amino chlorobenzene, which has prepared as described in the foregoing example, isintroduced into 0.70 mol "-(81.5 g). of N,N-diethylethylenediamine which has first been heated to C. The reaction mixture is heated for half an hour in a Analysis Calculated for Found c u mo s Cl NF/r Il.85 ll.7l|l.82 s /l 6.77 6.97 6.98

Several examples will now be given showing how the compounds of formula l are used in hair dyeing compositions.

EXAMPLE I8 The following composition is prepared:

l-N-fi-diethylaminoethylamino-Z-nitro-4N '-hydroxyethylamino benzene dihydrochloride 0.37g l-N-I-hydroxypropylamino-2-nitro-4-( N-methyl-N- acetyl) amine benzene 0.26g Isooctylphenylpolyethoxyethanol l.2g Na,c0,. q.s.p. pH 8 Water. q.s.p. 100g This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and shampooed.

A copper mahogany color results.

EXAMPLE 19 The following composition is prepared:

l-N-F-hydroxypropylamino-Z-nitro-4-( N-methyl-N- acetyl)-amino benzene 1.3g lsooctylphenylpolyethoxyethanol l.5g NH OH. q.s.p. pH 9 Water. q.s.p. lOOg This composition is applied to 100% white hair for 15 minutes. The hair is then rinsed and shampooed and a deep blonde shade results.

EXAMPLE 20 The following dyeing composition is prepared:

l-diethylaminoethylamino-2-nitro-4-N,N- dihydroxyethylamino benzene dihydrochloride 0.30g Methyl-fi-[N( 2-nitro-4-N'-methyl-N- benzenesulfonyl-amino)-phenyll-aminoethylmethyldiethylammonium sulfate 0.l4g Isooctyl phenyl polyethoxy ethanol 1.2g Monoethanolamine. q.s.p. pH 7.5 Water. q.s.p. 100g This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and shampooed.

A deep mahogany blond results.

12 EXAMPLE 21 The following dyeing composition is prepared:

l-Nfi diethylaminoethyl amino-2-nitro-4N'- hydroxyethylamino benzene 0.25g lsooctyl phenyl polycthoxyethanol l.2g Lactic acid q.s.p. pH 4 Water q.s.p. g

This composition is applied to bleached hair and left thereon for 10 minutes. The hair is then rinsed and shampooed.

A purple violet color results.

The dyes of the invention can be also applied to normal colored hair and without using an oxidizing agent.

The following dye compounds illustrate the compounds of the invention containing respectively the R Z R R" R, R and R radicals as before mentioned: l-N- B-hydroxyethylamino-2-nitro-4-(N-methyl-N-benzenesulfonyl)amino benzene l-N-B-diethylaminoethylamino-2-nitro-4-(N'-B-hydroxyethyl-N-benzenesulfonyl)-amino benzene 2-nitro-4-(N-acetyl-N- B-acetoxyethyl) -amino chlorobenzene methylaminol,nitro-2,( N,N-methyl, carboxymethyl)amino-4,benzene N-methylamino-l,nitro-2,(Nbenzenesulf0nyl,- N-B-bromoethyl)-amino-4, benzene 2-nitro- 4-N-(B-diethylaminoethyl)-amino chlorobenzene 1- N-B-diethylaminoethylamino-2-nitro-4(N'-B-diethylaminoethyl-N-benzenesulfonyl)amino benzene l-N-y-methoxypropylamino-2-nitro-4-(N-methyl-N'- benzenesulfonyl)amino benzene l-N-B-diethylaminoethylamino-2-nitro-4-(N'-methyl-N-benzenesulfonyl) amino benzene.

The following organic solvents may be used as solvent in the dye composition of this invention benzylic alcohol, phenethyl alcohol, 2-butoxyethanol, cyclohexanol and the like.

The ingredients which may be added to the dye composition of this invention of the convention type and particulary of the dyes selected from the group consisting of nitro dyes such as I-hydroxy-2-amino-5-nitro benzene, azo dyes such as Supracide (Compagnie Francaise des Matieres 'Colorantes),

Supramino (Socit Bayer),

Cibacte (Socit Ciba) et Solacete (Imperial Chemical Industries Ltd), and anthraquinone dyes such as:

Solway (Imperial Chemical Industries Ltd.),

Collit" (B.A.S.F.) et

Fenacet (General Dye Corp. N.Y.), and the like.

The following compounds illustrate the intermediate compounds of the invention I-chloro-2-nitro-4-(N-methyl-N-acetyl)-amino benzene l-chIoro-2-nitro-4-( N-methyl-N-benzenesulfonly amino benzene;

I-chloro-2-nitro-4-( N '-diethylaminoethyl-N 'benzenesulfonyl) amino benzene;

l chloro-2-nitro-4-(N-carbomethoxy-ethyl-N-acetyl) amino benzene I chloro-2-nitro-4-(N-carbethoxy-ethyl-N-benzenesulfonyl) amino benzene I chloro-2-nitro-4-(N-bromoethyl-N-benzenesulfonyl)amino benzene, and they have the respective formules oocu What is claimed is: having 1-6 carbon atoms and haloalkyl having l6 car- I. A compound selected from the group consisting of hen atoms; a. a compound of the formula X represents chlorine; and

Z is

wherein R is selected from the group consisting of X hydrogen, methyl and N0 and b. the hydrohalide of the compound in (a).

NRZ

wherein R is selected from the group consisting of lower alkyl having 1-6 carbon atoms, hydroxy alkyl 

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A. A COMPOUND OF THE FORMULA 